Professional Documents
Culture Documents
6 (2007), 867-873
Original Research
Characterization of Leather Industry Wastes
H. Ozgunay*, S. Colak, M.M. Mutlu, F. Akyuz
Department of Leather Engineering, Faculty of Engineering, Ege University, 35100 Bornova, Izmir, Turkey
Abstract
In this research samples from solid wastes coming out from various process steps during manufacturing
of garment sheep skins, shoe upper goat skins, shoe upper hides and sole leathers have been collected. These
samples have been classified among themselves and their characteristics have been determined by various
chemical analysis. By characterization of solid wastes which state problems for the environment and costs
for treatment; data have been obtained which can be used for new management and evaluation methods.
Table 1: Estimated amount of solid (protein, tanned and un- removal of unwanted proteins from the hide. Follow-
tanned) waste during the processing of 1 ton of salted hides ac- ing the bating process, a degreasing process is applied
cording to various authors to hides for removing the excess natural fat in their
structure and providing a homogeneous distribution of
Püntener Alexander Buljan the fat in it.
Untanned waste: ii. Tanning Processes:
shavings The hides at this stage are first treated with pickle pro-
subepidermal Tissue 530 kg 120 kg 100 kg cess in a solution composed of salt and acids so as to
trimmings 135 kg 70-230 kg 300kg obtain a homogeneous distribution of tanning materi-
Tanned Waste: als through the cut. After the hides are conditioned as
shavings 145 kg 100 kg 99 kg above, the tanning process is applied with various tan-
split 115 107 ning materials (materials able to form stable bonds with
Dyed and finished waste: collagen) in order to provide the leather with a stable
shavings 10 kg 32 kg 10 kg
form and high thermal stability. Tanning materials such
fluff 2 kg 1 kg
as vegetable tannins, mineral tanning materials and
Total 870 kg 439-599 kg 637 kg syntans (synthetic organic tanning materials) are used
in tannage. Among mineral tanning materials, chrome
is the most widely used in leather production due to its
unique features that it gives to the leather. Aluminium
and vegetable tanning materials are also widely used in
leather production.
Before the leathers are treated with further processes,
the setting out and samming process is applied, and
shaving is done to obtain the desired thickness of the
leather.
iii. Post-Tanning Processes:
The next step for the leathers, which are tanned and
standardized to a desired thickness, is retannage pro-
cess with various retanning agents improving the re-
quested characteristics of products. In this process,
structural differences within leathers are compensated
Fig. 1. Amounts of leather industry raw material input and solid to obtain uniform structure. The Fatliquoring process
waste output. is applied by using a combination of various fatliquor-
ing agents in order to allow the leather to be more
supple and softer. In the dyeing process leathers are
It is possible to divide leather industry processes of dyed to the desired color. After this stage, leathers are
transforming rawhide into leather into four main stages: hanged and dried, and they are prepared for the fin-
i. Beamhouse processes: ishing process through certain mechanical operations.
The conserved hides are first subjected to a trim- The unwanted parts are trimmed and removed.
ming process for removing the unwanted parts, and iv. Finishing Processes:
then they are soaked to restore the lost water and to After the leathers are fatliquored and dyed following
remove substances like dirt, blood and conservation the tanning process, they are processed with a series
salt. After the wetted hides are fleshed to remove the of coatings on the surface in order to improve their
excess flesh and fat adhering to the hide (hypoder- resistance and produce appealing and uniform surface
mis), they are treated with an intense alkali solution of effects. After this process, leathers are trimmed for a
lime (Ca(OH)2) and sodium sulphide (Na2S) to ensure final form and sent to confection.
hair and wool removal (unhairing process). Later the
hides are swelled up in liming process by immersing Solid wastes generated by the leather industry in these
them in a strong alkaline bath so as to open up the stages of processes may be classified as follows:
collagen structure. The hides may be treated with a i. wastes from untanned hides/skins (trimmings, flesh-
second fleshing process after liming in order to clean ing wastes)
the flesh. At this stage, hides are treated with splitting ii. wastes from tanned leather (shaving wastes, buffing
process and split into two or three layers. Deliming is dust)
then performed to decrease the pH level in order to iii. wastes from dyed and finished leather (trimmings
remove the lime and to make the hide more receptive from leather)
to the chemicals that will be used in further stages. Data obtained from research reveals that 80% of solid
Through bating process, hides are exposed to an enzy- wastes are generated during pre-tanning processes, while
matic effect for both opening up the structures, and the 20% of the wastes are caused by post-tanning processes
Characterization of Leather... 869
[5]. Due to the bad smell they produce during their pu- 2: Lime fleshing waste
trefaction and their harmful chemical content, untanned 3: Shaving waste
hide/skin wastes have negative effects on the soil and/or 4: Buffing waste
water resources of the environment where they are dis- 5: Leather trimmings
charged, in other words on the local plant flora and animal Example: A1: Sheep skin pre-fleshing waste.
fauna. Therefore, uncontrolled discharge of such wastes
should be prevented without taking adequate precautions.
Legal arrangements gradually gaining speed all over the Method
world enforce the leather industry to apply innovations
in terms of reusing solid wastes generated during leather Solid waste samples examined for the study were ran-
production processes such as fleshing, shaving, trimming domly selected among piles in 2 different leather factories
and splits. manufacturing products for each leather type. Pre-fleshing
The most significant approach in preventing environ- and lime fleshing wastes, which are defined as untanned
mental pollution is the idea that prevention is better than wastes, were scrapped after the water in their structure was
reuse, reuse is better than recycling, and recycling is better removed (to a certain extent) in airy conditions, and then
than disposing of the wastes [6]. In other words, cleaner they were equally mixed and dried at 50-55°C. Shaving,
production. On this account, in order to provide cleaner buffing and leather trimmings from tanned leather wastes
production, the producers are supposed to prevent or re- were ground and mixed before they were dried at 102°C ±
duce waste formation by using clean technology during 2°C and prepared for chemical analyses. All other analy-
production processes, and transform the inevitable small ses (excluding water content measurement) were done by
amounts of waste into environmentally friendly materials. taking sufficient amounts from these samples.
Solid wastes create a major problem for leather in- The analysis were carried out using the following
dustry in terms of both their variety and quantity. A high standard methods: The amount of water content (volatile
amount of reusable waste is generated in the leather in- components) according to IUC 5 [8], pH according to
dustry. It is possible to recycle these products and even SLC 13 [8], Substances (fats and other substances) solu-
use them as raw materials for different industries [7]. The ble in dichloromethane according to SLC 4 [8], Nitrogen
variety and quantity of solid wastes depends on animal content according to Kjeldahl Method, Sodium chloride
species, breeding conditions, slaughterhouse practices, content according to SLC 402 [8], Sulphide content ac-
conservation conditions, leather process stages, mechani- cording to Monier-Williams Method.
cal operations, qualification of the personnel, and chemi- Thermal value of the samples were measured in Ber-
cals used in processes. Yet this fact causes uncertainties in tholet calorimeter under 23-30 atmosphere pressure by
reusing the generated wastes. burning with electric current in an aerobic environment
First of all, solid wastes should be characterized so and monitoring the temperature increase of a certain
that they can be reused. In this study, wastes from differ- amount of water by the generated heat.
ent companies have been analyzed with various chemical In order to determine Cr, Fe, Na, and Ca in waste sam-
and instrumental analysis methods, and their characteris- ples using an atomic absorption spectrophotometer, the
tics have been defined. This data is thought to be useful samples were first treated with an acid digestion process.
in terms of preventing both environmental pollution and Sample solutions were filled up to 100 ml with pure water
waste of resources by putting solid wastes into good use after they reached room temperature (it may be filtered
as secondary raw material in different industries rather through filter paper if necessary). Desired measurements
than transferring them to disposal areas. were later done in these obtained solutions by using atom-
ic absorption.
Cr, Fe, Na and Ca amounts of wastes were detected
Materials and Methods with Perkin-Elmer 2380 Atomic Absorption Spectropho-
tometer. Cr was measured at 357.9nm with 0.7 slit in-
Materials tervals by using air+C2H2 mixture, Fe was measured at
248.3nm with 0.2 slit intervals by using air+C2H2 mixture,
Samples of wastes from pre-fleshing, lime fleshing, Na was measured at 589.6nm with 1.4 slit intervals by us-
shaving, buffing and trimming, which were examined ing air+propane mixture and Ca was measured at 422.7nm
within the scope of the study, had been obtained from var- with 1.4 slit intervals by using air+C2H2 mixture.
ious factories producing different leather types (clothing
sheep skin, shoe upper goat skin, shoe upper hide and sole
cattle hide). Samples are coded as follows: Results and Discussion
A: Sheep skin
B: Goat skin Water Content
C: Hide (shoe upper)
D: Hide (sole) According to the results of water content determi-
1: Pre-fleshing waste nation in solid waste, water content was found to be
870 Ozgunay H. et al.
45-59% in pre-fleshing waste, 57-83% in lime flesh- cals in leather waste into soil and surface/ground waters
ing waste, 45-66% in shaving waste, 7-14% in buffing causes the deterioration of the natural structures of these
waste, and 6-9% in leather wastes. Sempere et al. [9] receiver environments. Especially in the case of wastes
have observed that water content of leather waste (18- including chrome, researchers have reported the infusion
25%) is lower than the water content of shaving waste of chrome into plants and ground waters [9].
(45-57%).
The obtained data reveal that fleshing and shaving
wastes include higher amounts of water in comparison pH
to other waste types. This result is due to the fact that
fleshing and shaving wastes are generated during leath- It has been observed that solid wastes show similari-
er process steps called beamhouse processes, in which ties in parallel with the process stages disclosing the pH
leathers are processed in watery environments. Water values of solid wastes, and the pH values at which these
content of solid wastes like buffing and trimming are processes are carried out; and it was found that liming
lower, since they are generated during the stages of dry fleshing waste has the highest pH value, since the liming
processes. process is done at around pH 11-12.
Water content of solid wastes differs to a great extent Acid-base reactions are among the most important
in accordance with how and where they are collected, matters regarding the environment. Most of the living
storage conditions, and climate. Yet there is always an ob- organisms are very sensitive to environmental pH. An-
vious water content difference between the wastes gener- other situation is that, when pH is forced to extreme lim-
ated during wet and dry processes. Water content of solid its, chemical balance reactions slide to the left or right,
wastes is of great significance at the time of storage and causing the occurrence of undesired sediments or gases.
use. Hence, in order to protect the current ecosystem, wastes
Due to the high amount of water in leather wastes, or should be subjected to a neutralization process before they
natural factors like rain or snow, infusion of the chemi- are disposed to the environment.
Characterization of Leather... 871
The Amount of Substances (Fats and Other to a great extent by treating the samples with alkali or
Solubles) Soluble in Dichloromethane with the help of enzymes, and thus protein hydrolysates
without chrome may be obtained (<5ppm). Therefore, it
Unless the fat in rawhide structure is removed, it af- is possible to put shaving wastes into commercial use due
fects other processes in a negative way by prohibiting to its wide area of use such as leatherboard, fertilizer or
the penetration of chemicals into the hide in further pro- hydrolysate production [11, 12].
cesses, and may also cause a strong smell, an increase in When other data were examined, nitrogen content of
micro-organism activity and defects like spew on leathers. the wastes from sole leather measuring 26-31% was found
For this reason, vast amounts of fat in hides are removed to be lower than the nitrogen contents of other waste types.
before tanning by applying a degreasing process. Bienkie- Since the rate of vegetable tanning substance in the waste
wicz [10] noted that fat content varies between 0.5% and (polyphenolic substance) increased, the nitrogen amount
4% in cattle and horse hides, 3% and 30% in sheep skin, detected in leather decreased accordingly.
4% and 40% in pig skin, and 3% and 10% in goat skin
over dry weights.
Another fat source in solid wastes is the natural or Sodium Chloride Content
synthetic fats used in the fatliquoring process in order
to provide the leather with features like softness, elastic- When the salt contents of solid wastes were examined,
ity and resistance, and to allow the leather fibers to slide it was found that salt proportions in most samples vary be-
easily over one another according to the leather type and tween 1% and 2.5%. As a matter of fact, it is remarkable
purpose of use. The fat content of leathers consists of the that salt contents of shaving wastes from all skin types
remaining natural fat after degreasing process, and the fat are higher than the average values of other samples, and
used in fatliquoring process. Due to this reason, different this difference is thought to stem from the high rate of
fat proportions may be detected in leather wastes. alkali salts used especially in basification at the end of the
In the research, it has been observed that pre-fleshing chrome tanning process; since this parallelism detected in
and lime fleshing wastes from the processes before de- shaving wastes is not observed in the shaving wastes from
greasing include higher amounts of fat compared to other sole leather treated with vegetable tanning process.
waste samples (40-70%). In addition, it should be kept in The high content of salt in solid wastes causes an in-
mind that wastes were generated at the end of the flesh- crease in the salt amount of the soil where these wastes
ing process that was applied to remove the hypodermis are stored. Soluble salts have negative effects on plant
layer of the hide, which is the layer including the highest growth, because the intake of nutritional elements by
amount of fat. It should also be taken into consideration the plant is prohibited due to ion competition when the
that flesh and fat layers left on hides may differ greatly, soil contains high amounts of cation and anions. This salt
depending on slaughter and flaying techniques, which in damage emerges because of the insufficiency of nutrition-
turn directly affects the fat amount in waste. This high al elements. Additionally, high salinity or total dissolved
amount of fat in fleshing waste may be evaluated in differ- salts in water causes high osmotic pressure, which results
ent fields such as the chemical industry, soap production, in reduced water availability to plants and retarded plant
biodiesel production, and the production of fatliquors [7]. growth of crops which are not salt tolerant [13].
The fat obtained from lime fleshing waste is generally re-
garded to be of low quality due to its dirty colour and bad
smell resulting from sulphide contact. Sulphide Content
conditions, require pickling and more buffer salts. Simi- 4. FAO. Statistics. http://faostat.fao.org/faostat, (July 20,
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